Agglomeration process for producing detergent compositions involving premixing modified polyamine polymers

ABSTRACT

A process for producing an agglomerated detergent composition comprises premixing an acid precursor of a detersive surfactant and a water-soluble or dispersible, modified polyamine in a mixer to form a premix, inputting the premix and dry detergent materials such as builders into a high speed mixer/densifier and neutralizing the acid precursor to form agglomerates and further agglomerating in a moderate speed mixer/densifier to form a detergent composition having a bulk density of at least 650 g/l.

This application claims the benefit of U.S. Provisional Application No.60/024,800, filed Aug. 26, 1996.

FIELD OF THE INVENTION

The present invention relates to an agglomeration process for producinglaundry detergent compositions that contain modified polyaminesespecially useful as cotton soil release and/or dispersant agents. Morespecifically, the process involves premixing the modified polyamine witha surfactant paste or an acid precursor thereof prior to subsequentagglomeration with a builder and optional adjunct detergent ingredients.The premixture is subjected to an agglomeration step which can becarried forth in a two serially positioned mixer/densifiers so as toprovide an agglomerated detergent composition having improvedperformance.

BACKGROUND OF THE INVENTION

Various fabric surface modifying agents have been commercialized and arecurrently used in detergent compositions and fabric softener/antistaticarticles and compositions. Examples of surface modifying agents are soilrelease polymers. Soil release polymers typically comprise an oligomericor polymeric ester "backbone" and are generally very effective onpolyester or other synthetic fabrics where the grease or similarhydrophobic stains form an attached film and are not easily removed inan aqueous laundering process. The soil release polymers have a lessdramatic effect on "blended" fabrics, that is, on fabrics that comprisea mixture of cotton and synthetic material, and have little or no effecton cotton articles.

Extensive research in this area has yielded significant improvements inthe effectiveness of polyester soil release agents yielding materialswith enhanced product performance and capability of being incorporatedinto detergent formulations. Modifications of the polymer backbone aswell as the selection of proper end-capping groups have produced a widevariety of polyester soil release polymers. For example, end-capmodifications, such as the use of sulfoaryl moieties and especially thelow cost isethionate-derived end-capping units, have increased the rangeof solubility and adjunct ingredient compatibility of these polymerswithout sacrifice to soil release effectiveness. Many polyester soilrelease polymers can now be formulated into both liquid as well as solid(i.e., granular) detergents.

As in the case of polyester soil release agents, producing an oligomericor polymeric material that mimics the structure of cotton has notresulted in a cotton soil release polymer. Although cotton and polyesterfabric are both comprised of long chain polymeric materials, they arechemically very different. Cotton is comprised of cellulose fibers thatconsist of anhydroglucose units joined by 1-4 linkages. These glycosidiclinkages characterize the cotton cellulose as a polysaccharide whereaspolyester soil release polymers are generally a combination ofterephthalate and ethylene/propylene oxide residues. These differencesin composition account for the difference in the fabric properties ofcotton versus polyester fabric. Cotton is hydrophilic relative topolyester. Polyester is hydrophobic and attracts oily or greasy dirt andcan be easily "dry cleaned". Importantly, the terephthalate andethyleneoxy/propyleneoxy backbone of polyester fabric does not containreactive sites, such as the hydroxyl moieties of cotton, that react withstains in a different manner than synthetics. Many cotton stains become"fixed" and can only be resolved by bleaching the fabric.

Until recently, the development of effective fabric surface modifyingagents for use on cotton fabrics has been elusive. Attempts by others toapply the paradigm of matching the structure of a soil release polymerwith the structure of the fabric, a method successful in the polyestersoil release polymer field, have nevertheless yielded marginal resultswhen applied to other fabric surface modifying agents, especially forcotton fabrics. For example, the use of methylcellulose, a cottonpolysaccharide with modified oligomeric units, proved to be moreeffective on polyesters than on cotton.

Additionally, detergent formulators have been faced with the task ofdevising products to remove a broad spectrum of soils and stains fromfabrics. The varieties of soils and stains ranges within a spectrumspanning from polar soils, such as proteinaceous, clay, and inorganicsoils, to non-polar soils, such as soot, carbon-black, by-products ofincomplete hydrocarbon combustion, and organic soils. To that end,detergent compositions have become more complex as formulators attemptto provide products which handle all types of such soils concurrently.Formulators have been highly successful in developing traditionaldispersants which are particularly useful in suspending polar, highlycharged, hydrophilic particles such as clay. As yet, however,dispersants designed to disperse and suspend non-polar, hydrophobic-typesoils and particulates have been more difficult to develop.

It has been surprisingly discovered that effective soil release agentsfor cotton articles and dispersants can be prepared from certainmodified polyamines. This unexpected result has yielded compositionsthat are key to providing these benefits once available to onlysynthetic and synthetic-cotton blended fabric. However, the manner inwhich such modified polyamines may be included into fully formulateddetergent compositions so as to retain, and preferably, improveperformance has remained unresolved. Detergent compositions whichcontain these modified polyamines and are produced via prior artprocesses do not perform at the desired level of performance.Accordingly, there remains a need in the art for a detergent-makingprocess which provides a means by which selected modified polyamines canbe incorporated into fully formulated detergent compositions that haveenhanced cleaning performance.

BACKGROUND ART

U.K. 1,314,897. published Apr. 26, 1973 teaches a hydroxypropyl methylcellulose material for the prevention of wet-soil redeposition andimproving stain release on laundered fabric. U.S. Pat. No. 3,897,026issued to Kearney, discloses cellulosic textile materials havingimproved soil release and stain resistance properties obtained byreaction of an ethylene-maleic anhydride co-polymer with the hydroxylmoieties of the cotton polymers. U.S. Pat. No. 3,912,681 issued toDickson teaches a composition for applying a non-permanent soil releasefinish comprising a polycarboxylate polymer to a cotton fabric. U.S.Pat. No. 3,948,838 issued to Hinton, et alia describes high molecularweight (500,000 to 1,500,000) polyacrylic polymers for soil release.U.S. Pat. No. 4,559,056 issued to Leigh, et alia discloses a process fortreating cotton or synthetic fabrics with a composition comprising anorganopolysiloxane elastomer, an organosiloxaneoxyalkylene copolymercrosslinking agent and a siloxane curing catalyst. See also U.S. Pat.Nos. 4,579,681 and 4,614,519. These disclose vinyl caprolactam materialshave their effectiveness limited to polyester fabrics, blends of cottonand polyester, and cotton fabrics rendered hydrophobic by finishingagents.

In addition to the above cited art, the following disclose various soilrelease polymers or modified polyamines; U.S. Pat. No. 4,548,744,Connor, issued Oct. 22, 1985; U.S. Pat. No. 4,597,898, Vander Meer,issued Jul. 1, 1986; U.S. Pat. No. 4,877,896, Maldonado, et al., issuedOct. 31, 1989; U.S. Pat. No. 4,891,160, Vander Meer, issued Jan. 2,1990; U.S. Pat. No. 4,976,879, Maldonado, et al., issued Dec. 11, 1990;U.S. Pat. No. 5,415,807, Gosselink, issued May 16, 1995; U.S. Pat. No.4,235,735, Marco, et al., issued Nov. 25, 1980; U.K. Patent 1,537,288,published Dec. 29, 1978; U.K. Patent 1,498,520, published Jan. 18, 1978;WO 95/32272, published Nov. 30, 1995; European Patent Application206,513; German Patent DE 28 29 022, issued Jan. 10, 1980; JapaneseKokai JP 06313271, published Apr. 27, 1994.

The following references are directed to densifying spray-driedgranules: Appel et al, U.S. Pat. No. 5,133,924 (Lever); Bortolotti etal, U.S. Pat. No. 5,160,657 (Lever); Johnson et al, British patent No.1,517,713 (Unilever); and Curtis, European Patent Application 451,894.The following references are directed to producing detergents byagglomeration: Capeci et al, U.S. Pat. No. 5,366,652, issued Nov. 22,1994 and Capeci et al, U.S. Pat. No. 5,486,303, issued Jan. 23, 1996;Beerse et al, U.S. Pat. No. 5,108,646 (Procter & Gamble); Hollingsworthet al, European Patent Application 351,937 (Unilever); and Swatling etal, U.S. Pat. No. 5,205,958.

SUMMARY OF THE INVENTION

The aforementioned needs in the art are met by the present inventionwhich provides a process in which selected modified polyamines areincorporated into fully formulated detergent compositions thatunexpectedly exhibit enhanced dispersancy and cleaning performanceespecially relative to cotton-containing fabrics. In essence, theprocess invention involves premixing the modified polyamine with adetersive surfactant or acid precursor thereof, and thereafter,agglomerating the premix in a high speed mixer/densifier followed by amoderate speed mixer/densifier with builders and optional adjunctdetergent ingredients.

In accordance with one aspect of the invention, a process for anagglomerated detergent composition is provided. The process comprisesthe steps of: (a) premixing a detersive surfactant paste, dry detergentmaterial and a water-soluble or dispersible, modified polyamine in apremixer to form a premix, the modified polyamine having a polyaminebackbone corresponding to the formula: ##STR1## having a modifiedpolyamine formula V.sub.(n+1) W_(m) Y_(n) Z or a polyamine backbonecorresponding to the formula: ##STR2## having a modified polyamineformula V.sub.(n-k+1) W_(m) Y_(n) Y'_(k) Z, wherein k is less than orequal to n, the polyamine backbone prior to modification has a molecularweight greater than about 200 daltons, wherein i) V units are terminalunits having the formula: ##STR3## ii) W units are backbone units havingthe formula: ##STR4## iii) Y units are branching units having theformula: ##STR5## iv) Z units are terminal units having the formula:##STR6## wherein backbone linking R units are selected from the groupconsisting of C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, C₃ -C₁₂hydroxyalkylene, C₄ -C₁₂ dihydroxy-alkylene, C₈ -C₁₂ dialkylarylene,--(R¹ O)_(x) R¹ --, --(R¹ O)_(x) R⁵ (OR¹)_(x) --, --(CH₂ CH(OR²)CH₂O)_(z) (R¹ O)_(y) R¹ (OCH₂ CH(OR²)CH₂)_(w) --, --C(O)(R⁴)_(r) C(O)--,--CH₂ CH(OR²)CH₂ --, and mixtures thereof; wherein R¹ is C₂ -C₆ alkyleneand mixtures thereof; R² is hydrogen, --(R¹ O)_(x) B, and mixturesthereof; R³ is C₁ -C₁₈ alkyl, C₇ -C₁₂ arylalkyl, C₇ -C₁₂ alkylsubstituted aryl, C₆ -C₁₂ aryl, and mixtures thereof; R⁴ is C₁ -C₁₂alkylene, C₄ -C₁₂ alkenylene, C₈ -C₁₂ arylalkylene, C₆ -C₁₀ arylene, andmixtures thereof; R⁵ is C₁ -C₁₂ alkylene, C₃ -C₁₂ hydroxyalkylene, C₄-C₁₂ dihydroxy-alkylene, C₈ -C₁₂ dialkylarylene, --C(O)--, --C(O)NHR⁶NHC(O)--, --R¹ (OR¹)--, --C(O)(R⁴)_(r) C(O)--, --CH₂ CH(OH)CH₂ --, --CH₂CH(OH)CH₂ O(R¹ O)_(y) R¹ OCH₂ CH(OH)CH₂ --, and mixtures thereof; R⁶ isC₂ -C₁₂ alkylene or C₆ -C₁₂ arylene; E units are selected from the groupconsisting of hydrogen, C₁ -C₂₂ alkyl, C₃ -C₂₂ alkenyl, C₇ -C₂₂arylalkyl, C₂ -C₂₂ hydroxyalkyl, --(CH₂)_(p) CO₂ M, --(CH₂)_(q) SO₃ M,--CH(CH₂ CO₂ M)CO₂ M, --(CH₂)_(p) PO₃ M, --(R¹ O)_(x) B, --C(O)R³, andmixtures thereof; oxide; B is hydrogen, C₁ -C₆ alkyl, --(CH₂)_(q) SO₃ M,--(CH₂)_(p) CO₂ M, --(CH₂)_(q) (CHSO₃ M)CH₂ SO₃ M, --(CH₂)_(q) --(CHSO₂M)CH₂ SO₃ M, --(CH₂)_(p) PO₃ M, --PO₃ M, and mixtures thereof; M ishydrogen or a water soluble cation in sufficient amount to satisfycharge balance; X is a water soluble anion; m has the value from 4 toabout 400; n has the value from 0 to about 200; p has the value from 1to 6, q has the value from 0 to 6; r has the value of 0 or 1; w has thevalue 0 or 1; x has the value from 1 to 100; y has the value from 0 to100; z has the value 0 or 1; and (b) agglomerating the premix initiallyin a high speed mixer/densifier and subsequently in a moderate speedmixer/densifier so as to form agglomerates, thereby resulting in thedetergent composition.

In accordance with another aspect of the invention, a process forproducing an agglomerated detergent composition. This process comprisesthe steps of: (a) premixing an acid precursor of a detersive surfactant,dry detergent material and a water-soluble or dispersible, modifiedpolyamine in a mixer to form a premix, wherein the modified polyaminehas a polyamine backbone as described above; (b) inputting the premixinto a high speed mixer/densifier and neutralizing the acid precursor toform agglomerates; and (c) agglomerating the agglomerates further in amoderate speed mixer/densifier so as to form the detergent composition.Also provided by the invention are the detergent compositions made byany of the processes described herein.

As used herein, the term "agglomerates" refers to particles formed byagglomerating detergent granules or particles which typically have asmaller median particle size than the formed agglomerates. All documentscited herein are incorporated by reference, and all percentages usedherein are expressed as "percent-by-weight" unless indicated otherwise.All viscosities described herein are measured at 70° C. and at shearrates between about 10 to 100 sec⁻¹.

Accordingly, it is an object of the invention to provide a process forproducing an agglomerated detergent composition which provides a meansby which selected modified polyamine can be incorporated into fullyformulated detergent compositions. It is also an object of the inventionto provide such a process which minimizes or eliminates degradation ofthe selected modified polyamines as a result of the fully formulateddetergent-making process so as to provide enhanced cleaning performance.These and other objects, features and attendant advantages of thepresent invention will become apparent to those skilled in the art froma reading of the following detailed description of the preferredembodiment and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

The process of the instant invention involves premixing selectedmodified polyamines and a surfactant paste prior to, or during,neutralization of an acid precursor of a surfactant. While not intendingto be bound by theory, it is believed that the selected modifiedpoly-amines described more fully hereinafter form a complex with thedetersive surfactant in the surfactant paste or liquid acid precursorthereof. In order to achieve the maximum benefits of the process, thesurfactant paste will preferably comprise an anionic surfactant, andoptionally a nonionic surfactant, but preferably will not contain acationic surfactant. This polyamine/surfactant complex typically has ahigher oxidative degradation temperature as compared to the degradationtemperature of the modified polyamines by themselves. As a consequenceof this complex formation, the selected modified polyamines unexpectedlyresult in improved performance of the fully formulated granulardetergent composition into which these modified polyamines areincorporated.

To this end, the modified polyamine and surfactant paste or acidprecursor thereof is mixed for at least about 5 seconds, preferably fromabout 5 seconds to about 1 minute in any acceptable known mixingapparatus such as an in-line static mixer, twin-screw extruder, stirredmixing tanks and the like. The temperature at which the premixing stepusing the surfactant paste is performed typically is at a temperature offrom about 25° C. to about 80° C. Also, it is preferred to maintain thepH of the premix at from about 8 to about 10 without other detergentingredients other than the surfactant paste and modified polyamine. Inthe case of the use of an acid precursor, the pH is typically from about1 to about 3 and the temperature is typically from about 50° C. to about90° C. The modified polyamine is preferably present in an amount of fromabout 0.01% to about 10%, more preferably from about 0.05% to about 5%,and most preferably from about 0.1% to about 1.0%, by weight of theoverall detergent composition. Further, in the premixing step, thedetersive surfactant paste preferably comprises from about 1% to about70%, more preferably from about 20% to about 60%, and most preferablyfrom about 25% to about 50%, by weight of a detersive surfactant thebalance water and other minor ingredients. The preferred surfactantsused in the surfactant paste are anionic surfactants as detailedhereinafter. With the aforementioned selections, the process provides adetergent composition unexpectedly exhibits improved cleaningperformance as compared to direct addition of the modified polyamine tothe composition.

In the embodiment involving the surfactant paste, the premix of modifiedpolyamine and paste are initially agglomerated in a high speedmixer/densifier followed by a moderate speed mixer/densifier. The highspeed mixer/densifier is a Lodige CB 30 mixer or similar brand mixer.These types of mixers essentially consist of a horizontal, hollow staticcylinder having a centrally mounted rotating shaft around which severalplough-shaped blades are attached. Preferably, the shaft rotates at aspeed of from about 100 rpm to about 2500 rpm, more preferably fromabout 300 rpm to about 1600 rpm. Preferably, the mean residence time ofthe detergent ingredients in the high speed mixer/densifier ispreferably in range from about 2 seconds to about 45 seconds, and mostpreferably from about 5 seconds to about 15 seconds.

Preferably, the resulting detergent agglomerates formed in the highspeed mixer/densifier are then fed into a lower or moderate speedmixer/densifier during which further agglomeration and densification iscarried forth. This particular moderate speed mixer/densifier used inthe present process should include liquid distribution and agglomerationtools so that both techniques can occur simultaneously. It is preferableto have the moderate speed mixer/densifier be, for example, a Lodige KM600 (Ploughshare) mixer, Drais® K-T 160 mixer or similar brand mixer.The residence time in the moderate speed mixer/densifier is preferablyfrom about 0.5 minutes to about 15 minutes, most preferably theresidence time is about 1 to about 10 minutes. The liquid distributioncan be accomplished by cutters, generally smaller in size than therotating shaft, which preferably operate at about 3600 rpm. It should beunderstood that while the processing described herein is relative toformation of high density agglomerates, the same equipment andprocessing steps may be used to produce less or moderately denseagglomerates. Of course, agglomerates produced by the process regardlessof the density can be admixed with less dense spray-dried granules inthe final detergent product, if desired.

The detergent agglomerates produced by the process preferably have asurfactant level of from about 25% to about 55%, more preferably fromabout 35% to about 55% and, most preferably from about 45% to about 55%.The particle porosity of the resulting detergent agglomerates producedaccording to the process of the invention is preferably in a range fromabout 5% to about 20%, more preferably at about 10%. In addition, anattribute of dense or densified agglomerates is the relative particlesize. The present process typically provides detergent agglomerateshaving a median particle size of from about 400 microns to about 700microns, and more preferably from about 400 microns to about 600microns. As used herein, the phrase "median particle size" refers toindividual agglomerates and not individual particles or detergentgranules. The combination of the above-referenced porosity and particlesize results in agglomerates having density values of 650 g/l andhigher. Alternatively, the particle size and porosity can be adjusted toproduce agglomerates having lower densities, as well (e.g., 300 g/l to500 g/l). Such features are especially useful in the production of lowas well as high or conventional dosage laundry detergents as well asother granular compositions such as dishwashing compositions.

In the embodiment involving the acid precursor of a surfactant, thepremix of acid precursor and modified polyamine is neutralized with aneutralizing agent, preferably a dry agent selected from the groupconsisting of carbonates, silicates, sodium hydroxide and mixturesthereof, with sodium carbonate being the most preferred. Thisneutralization occurs in the high speed mixer/densifier previouslymentioned. If the surfactant paste is used, the neutralization step isnot necessary, and the dry detergent material is inputted into the highspeed mixer/densifier with the premix. In both embodiments, agglomeratesare formed in the high speed mixer/densifier. However, it is preferableto send these agglomerates to the aforementioned moderate speedmixer/densifier for further build-up of particle size and additionalagglomeration. Preferably, the dry detergent material includes sodiumsulfate and a detergent builder selected from the group consisting ofaluminosilicates, carbonates, phosphates and mixtures thereof. Optionaladjunct detergent ingredients as described more fully hereinafter can beadded in any step of the process to provide a more fully formulateddetergent composition.

Optional Process Steps

In an optional step of the present process, the detergent agglomeratesformed by the process are dried in a fluid bed dryer and/or furtherconditioned by cooling the agglomerates in a fluid bed cooler or similarapparatus as are well known in the art. Another optional process stepinvolves adding a coating agent to improve flowability and/or minimizeover agglomeration of the detergent composition in one or more of thefollowing locations of the instant process: (1) the coating agent can beadded directly after the fluid bed cooler or dryer; (2) the coatingagent may be added between the fluid bed dryer and the fluid bed cooler;(3) the coating agent may be added between the fluid bed dryer and themixer/densifier(s); and/or (4) the coating agent may be added directlyto one or more of the mixer/densifiers. The coating agent is preferablyselected from the group consisting of aluminosilicates, silicates,carbonates and mixtures thereof. The coating agent not only enhances thefree flowability of the resulting detergent composition which isdesirable by consumers in that it permits easy scooping of detergentduring use, but also serves to control agglomeration by preventing orminimizing over agglomeration, especially when added directly to themixer/densifier(s). As those skilled in the art are well aware, overagglomeration can lead to very undesirable flow properties andaesthetics of the final detergent product.

Other optional steps in the present process involve recycling oversizedand undersized agglomerates as described in Capeci et al, U.S. Pat. Nos.5,489,392 and 5,516,448 (Procter & Gamble). Also, the step of includingan anhydrous material at selected points in the process can beincorporated as described by Capeci et al, U.S. Pat. No. Nos. 5,366,652and 5,486,303 (Procter & Gamble). Optionally, the agglomerates exitingthe moderate speed mixer/densifier can be dried in a spray drying toweras described in Capeci et al, U.S. Pat. No. 5,496,487 (Procter &Gamble).

Optionally, the process can comprises the step of spraying an additionalbinder in the mixer/densifier(s). A binder is added for purposes ofenhancing agglomeration by providing a "binding" or "sticking" agent forthe detergent components. The binder is preferably selected from thegroup consisting of water, anionic surfactants, nonionic surfactants,polyethylene glycol, polyvinyl pyrrolidone polyacrylates, citric acidand mixtures thereof. Other suitable binder materials including thoselisted herein are described in Beerse et al, U.S. Pat. No. 5,108,646(Procter & Gamble), the disclosure of which is incorporated herein byreference.

Another optional step of the instant process entails finishing theresulting detergent agglomerates by a variety of processes includingspraying and/or admixing other conventional detergent ingredients. Forexample, the finishing step encompasses spraying on perfumes, and theaddition of brighteners and enzymes to the finished agglomerates toprovide a more complete detergent composition. Such techniques andingredients are well known in the art.

Modified Polyamines

The modified polyamines used in the process invention are water-solubleor dispersible, especially useful for cleaning cotton-containing fabricsor as a dispersant. These polyamines comprise backbones that can beeither linear or cyclic. The polyamine backbones can also comprisepolyamine branching chains to a greater or lesser degree. In general,the polyamine backbones described herein are modified in such a mannerthat each nitrogen of the polyamine chain is thereafter described interms of a unit that is substituted, quaternized, oxidized, orcombinations thereof.

For the purposes of the present invention the term "modification" isdefined as replacing a backbone --NH hydrogen atom by an E unit(substitution), quaternizing a backbone nitrogen (quaternized) oroxidizing a backbone nitrogen to the N-oxide (oxidized). The terms"modification" and "substitution" are used interchangeably whenreferring to the process of replacing a hydrogen atom attached to abackbone nitrogen with an E unit. Quaternization or oxidation may takeplace in some circumstances without substitution, but preferablysubstitution is accompanied by oxidation or Quaternization of at leastone backbone nitrogen.

The linear or non-cyclic polyamine backbones that comprise the polymersused in the process have the general formula: ##STR7## said backbonesprior to subsequent modification, comprise primary, secondary andtertiary amine nitrogens connected by R "linking" units. The cyclicpolyamine backbones have the general formula: ##STR8## said backbonesprior to subsequent modification, comprise primary, secondary andtertiary amine nitrogens connected by R "linking" units

For the purpose of the present invention, primary amine nitrogenscomprising the backbone or branching chain once modified are defined asV or Z "terminal" units. For example, when a primary amine moiety,located at the end of the main polyamine backbone or branching chainhaving the structure

H₂ N--R]--

is modified according to the present invention, it is thereafter definedas a V "terminal" unit, or simply a V unit. However, for the purposes ofthe present invention, some or all of the primary amine moieties canremain unmodified subject to the restrictions further described hereinbelow. These unmodified primary amine moieties by virtue of theirposition in the backbone chain remain "terminal" units. Likewise, when aprimary amine moiety, located at the end of the main polyamine backbonehaving the structure

--NH₂

is modified according to the present invention, it is thereafter definedas a Z "terminal" unit, or simply a Z unit. This unit can remainunmodified subject to the restrictions further described herein below.

In a similar manner, secondary amine nitrogens comprising the backboneor branching chain once modified are defined as W "backbone" units. Forexample, when a secondary amine moiety, the major constituent of thebackbones and branching chains of the present invention, having thestructure ##STR9## is modified according to the present invention, it isthereafter defined as a W "backbone" unit, or simply a W unit. However,for the purposes of the present invention, some or all of the secondaryamine moieties can remain unmodified. These unmodified secondary aminemoieties by virtue of their position in the backbone chain remain"backbone" units.

In a further similar manner, tertiary amine nitrogens comprising thebackbone or branching chain once modified are further referred to as Y"branching" units. For example, when a tertiary amine moiety, which is achain branch point of either the polyamine backbone or other branchingchains or rings, having the structure ##STR10## is modified according tothe present invention, it is thereafter defined as a Y "branching" unit,or simply a Y unit. However, for the purposes of the present invention,some or all or the tertiary amine moieties can remain unmodified. Theseunmodified tertiary amine moieties by virtue of their position in thebackbone chain remain "branching" units. The R units associated with theV, W and Y unit nitrogens which serve to connect the polyaminenitrogens, are described herein below.

The final modified structure of the polyamines of the present inventioncan be therefore represented by the general formula

    V.sub.(n+1) W.sub.m Y.sub.n Z

for linear polyamines, by the general formula

    V.sub.(n-k+1) W.sub.m Y.sub.n Y'.sub.k Z

for cyclic polyamine polymers. For the case of polyamines comprisingrings, a Y' unit of the formula ##STR11## serves as a branch point for abackbone or branch ring. For every Y' unit there is a Y unit having theformula ##STR12## that will form the connection point of the ring to themain polymer chain or branch. In the unique case where the backbone is acomplete ring, the polyamine backbone has the formula ##STR13##therefore comprising no Z terminal unit and having the formula

    V.sub.n-k W.sub.m Y.sub.n Y'.sub.k

wherein k is the number of ring forming branching units. Preferably thepolyamine backbones of the present invention comprise no rings.

In the case of non-cyclic polyamines, the ratio of the index n to theindex m relates to the relative degree of branching. A fullynon-branched linear modified polyamine according to the presentinvention has the formula

    VW.sub.m Z

that is, n is equal to 0. The greater the value of n (the lower theratio of m to n), the greater the degree of branching in the molecule.Typically the value for m ranges from a minimum value of 4 to about 400,however larger values of m, especially when the value of the index n isvery low or nearly 0, are also preferred.

Each polyamine nitrogen whether primary, secondary or tertiary, oncemodified according to the present invention, is further defined as beinga member of one of three general classes; simple substituted,quaternized or oxidized. Those polyamine nitrogen units not modified areclassed into V, W, Y, or Z units depending on whether they are primary,secondary or tertiary nitrogens. That is unmodified primary aminenitrogens are V or Z units, unmodified secondary amine nitrogens are Wunits and unmodified tertiary amine nitrogens are Y units for thepurposes of the present invention.

Modified primary amine moieties are defined as V "terminal" units havingone of three forms:

a) simple substituted units having the structure: ##STR14## b)quaternized units having the structure: ##STR15## wherein X is asuitable counter ion providing charge balance; and c) oxidized unitshaving the structure: ##STR16##

Modified secondary amine moieties are defined as W "backbone" unitshaving one of three forms:

a) simple substituted units having the structure: ##STR17## b)quaternized units having the structure: ##STR18## wherein X is asuitable counter ion providing charge balance; and c) oxidized unitshaving the structure: ##STR19##

Modified tertiary amine moieties are defined as Y "branching" unitshaving one of three forms:

a) unmodified units having the structure: ##STR20## b) quaternized unitshaving the structure: ##STR21## wherein X is a suitable counter ionproviding charge balance; and c) oxidized units having the structure:##STR22##

Certain modified primary amine moieties are defined as Z "terminal"units having one of three forms:

a) simple substituted units having the structure: ##STR23## b)quaternized units having the structure: ##STR24## wherein X is asuitable counter ion providing charge balance; and c) oxidized unitshaving the structure: ##STR25##

When any position on a nitrogen is unsubstituted of unmodified, it isunderstood that hydrogen will substitute for E. For example, a primaryamine unit comprising one E unit in the form of a hydroxyethyl moiety isa V terminal unit having the formula (HOCH₂ CH₂)HN--.

For the purposes of the present invention there are two types of chainterminating units, the V and Z units. The Z "terminal" unit derives froma terminal primary amino moiety of the structure --NH₂. Non-cyclicpolyamine backbones according to the present invention comprise only oneZ unit whereas cyclic polyamines can comprise no Z units. The Z"terminal" unit can be substituted with any of the E units describedfurther herein below, except when the Z unit is modified to form anN-oxide. In the case where the Z unit nitrogen is oxidized to anN-oxide, the nitrogen must be modified and therefore E cannot be ahydrogen.

The polyamines of the present invention comprise backbone R "linking"units that serve to connect the nitrogen atoms of the backbone. R unitscomprise units that for the purposes of the present invention arereferred to as "hydrocarbyl R" units and "oxy R" units. The"hydrocarbyl" R units are C₂ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, C₃ -C₁₂hydroxyalkylene wherein the hydroxyl moiety may take any position on theR unit chain except the carbon atoms directly connected to the polyaminebackbone nitrogens; C₄ -C ₁₂ dihydroxyalkylene wherein the hydroxylmoieties may occupy any two of the carbon atoms of the R unit chainexcept those carbon atoms directly connected to the polyamine backbonenitrogens; C₈ -C₁₂ dialkylarylene which for the purpose of the presentinvention are arylene moieties having two alkyl substituent groups aspart of the linking chain. For example, a dialkylarylene unit has theformula ##STR26## although the unit need not be 1,4-substituted, but canalso be 1,2 or 1,3 substituted C₂ -C₁₂ alkylene, preferably ethylene,1,2-propylene, and mixtures thereof, more preferably ethylene. The "oxy"R units comprise --(R¹ O)_(x) R⁵ (OR¹)_(x) --, --CH₂ CH(OR²)CH₂ O)_(z)(R¹ O)_(y) R¹ (OCH₂ CH(OR²)CH₂)_(w) --, --CH₂ CH(OR²)CH₂ --, --(R¹O)_(x) R¹ --, and mixtures thereof. Preferred R units are C₂ -C₁₂alkylene, C₃ -C₁₂ hydroxyalkylene, C₄ -C₁₂ dihydroxyalkylene, C₈ -C₁₂dialkylarylene, --(R¹ O)_(x) R¹ --, --CH₂ CH(OR²)CH₂ --, --(CH₂CH(OH)CH₂ O)_(z) (R¹ O)_(y) R¹ (OCH₂ CH--(OH)CH₂)_(w) --, --(R¹ O)_(x)R⁵ (OR¹)_(x) --, more preferred R units are C₂ -C₁₂ alkylene, C₃ -C₁₂hydroxyalkylene, C₄ -C₁₂ dihydroxyalkylene, --(R¹ O)_(x) R¹ --, --(R¹O)_(x) R⁵ (OR¹)_(x) --, --(CH₂ CH(OH)CH₂ O)_(z) (R¹ O)_(y) R¹ (OCH₂CH--(OH)CH₂)_(w) --, and mixtures thereof, even more preferred R unitsare C₂ -C₁₂ alkylene, C₃ hydroxyalkylene, and mixtures thereof, mostpreferred are C₂ -C₆ alkylene. The most preferred backbones of thepresent invention comprise at least 50% R units that are ethylene.

R¹ units are C₂ -C₆ alkylene, and mixtures thereof, preferably ethylene,R² is hydrogen, and --(R¹ O)_(x) B, preferably hydrogen.

R³ is C¹ -C₁₈ alkyl, C₇ -C₁₂ arylalkylene, C₇ -C₁₂ alkyl substitutedaryl, C₆ -C₁₂ aryl, and mixtures thereof, preferably C₁ -C₁₂ alkyl, C₇-C₁₂ arylalkylene, more preferably C₁ -C₁₂ alkyl, most preferablymethyl. R³ units serve as part of E units described herein below.

R⁴ is C₁ -C₁₂ alkylene, C₄ -C₁₂ alkenylene, C₈ -C₁₂ arylalkylene, C₆-C₁₀ arylene, preferably C₁ -C₁₀ alkylene, C₈ -C₁₂ arylalkylene, morepreferably C₂ -C₈ alkylene, most preferably ethylene or butylene.

R⁵ is C₁ -C₁₂ alkylene, C₃ -C₁₂ hydroxyalkylene, C₄ -C₁₂dihydroxyalkylene, C₈ -C₁₂ dialkylarylene, --C(O)--, --C(O)NHR⁶NHC(O)--, --C(O)(R⁴)_(r) C(O)--, --R¹ (OR¹)--, --CH₂ CH(OH)CH₂ O(R¹O)_(y) R¹ OCH₂ CH(OH)CH₂ --, --C(O)(R⁴)_(r) C(O)--, --CH₂ CH(OH)CH₂ --,R⁵ is preferably ethylene, --C(O)--, --C(O)NHR⁶ NHC(O)--, --R¹ (OR¹)--,--CH₂ CH(OH)CH₂ --, --CH₂ CH(OH)CH₂ O(R¹ O)_(y) R¹ OCH₂ CH--(OH)CH₂ --,more preferably --CH₂ CH(OH)CH₂ --.

R⁶ is C₂ -C₁₂ alkylene or C₆ -C₁₂ arylene.

The preferred "oxy" R units are further defined in terms of the R¹, R²,and R⁵ units. Preferred "oxy" R units comprise the preferred R¹, R², andR⁵ units. The preferred modified polyamines comprise at least 50% R¹units that are ethylene. Preferred R¹, R², and R⁵ units are combinedwith the "oxy" R units to yield the preferred "oxy" R units in thefollowing manner.

i) Substituting more preferred R⁵ into --(CH₂ CH₂ O)_(x) R⁵ (OCH₂CH₂)_(x) -- yields --(CH₂ CH₂ O)_(x) CH₂ CHOHCH₂ (OCH₂ CH₂)_(x) --.

ii) Substituting preferred R¹ and R² into --(CH₂ CH(OR²)CH₂ O)_(z) --(R¹O)_(y) R¹ O(CH₂ CH(OR²)CH₂)_(w) -- yields --(CH₂ CH(OH)CH₂ O)_(z) --(CH₂CH₂ O)_(y) CH₂ CH₂ O(CH₂ CH(OH)CH₂)_(w) --.

iii) Substituting preferred R² into --CH₂ CH(OR²)CH₂ -- yields --CH₂ CH₂(OH)CH₂ --.

E units are selected from the group consisting of hydrogen, C₁ -C₂₂alkyl, C₃ -C₂₂ alkenyl, C₇ -C₂₂ arylalkyl, C₂ -C₂₂ hydroxyalkyl,--(CH₂)_(p) CO₂ M, --(CH₂)_(q) SO₃ M, --CH(CH₂ CO₂ M)CO₂ M, --(CH₂)_(p)PO₃ M, --(R¹ O)_(m) B, --C(O)R³, preferably hydrogen, C₂ -C₂₂hydroxyalkylene, benzyl, C₁ -C₂₂ alkylene, --(R¹ O)_(m) B, --C(O)R³,--(CH₂)_(p) CO₂ M, --(CH₂)_(q) SO₃ M, --CH(CH₂ CO₂ M)CO₂ M, morepreferably C₁ -C₂₂ alkylene, --(R¹ O)_(x) B, --C(O)R³, --(CH₂)_(p) CO₂M, --(CH₂)_(q) SO₃ M, --CH(CH₂ CO₂ M)CO₂ M, most preferably C₁ -C₂₂alkylene, --(R¹ O)_(x) B, and --C(O)R³. When no modification orsubstitution is made on a nitrogen then hydrogen atom will remain as themoiety representing E.

E units do not comprise hydrogen atom when the V, W or Z units areoxidized, that is the nitrogens are N-oxides. For example, the backbonechain or branching chains do not comprise units of the followingstructure: ##STR27##

Additionally, E units do not comprise carbonyl moieties directly bondedto a nitrogen atom when the V, W or Z units are oxidized, that is, thenitrogens are N-oxides. According to the present invention, the E unit--C(O)R³ moiety is not bonded to an N-oxide modified nitrogen, that is,there are no N-oxide amides having the structure ##STR28## orcombinations thereof.

B is hydrogen, C₁ -C₆ alkyl, --(CH₂)_(q) SO₃ M, --(CH₂)_(p) CO₂ M,--(CH₂)_(q) --(CHSO₃ M)CH₂ SO₃ M, --(CH₂)_(q) (CHSO₂ M)CH₂ SO₃ M,--(CH₂)_(p) PO₃ M, --PO₃ M, preferably hydrogen, --(CH₂)_(q) SO₃ M,--(CH₂)_(q) (CHSO₃ M )CH₂ SO₃ M, --(CH₂)_(q) --(CHSO₂ M)CH₂ SO₃ M, morepreferably hydrogen or --(CH₂)_(q) SO₃ M.

M is hydrogen or a water soluble cation in sufficient amount to satisfycharge balance. For example, a sodium cation equally satisfies--(CH₂)_(p) CO₂ M, and --(CH₂)_(q) SO₃ M, thereby resulting in--(CH₂)_(p) CO₂ Na, and --(CH₂)_(q) SO₃ Na moieties. More than onemonovalent cation, (sodium, potassium, etc.) can be combined to satisfythe required chemical charge balance. However, more than one anionicgroup may be charge balanced by a divalent cation, or more than onemono-valent cation may be necessary to satisfy the charge requirementsof a poly-anionic radical. For example, a --(CH₂)_(p) PO₃ M moietysubstituted with sodium atoms has the formula --(CH₂)_(p) PO₃ Na₃.Divalent cations such as calcium (Ca²⁺) or magnesium (Mg²⁺) may besubstituted for or combined with other suitable mono-valent watersoluble cations. Preferred cations are sodium and potassium, morepreferred is sodium.

X is a water soluble anion such as chlorine (Cl⁻), bromine (Br⁻) andiodine (I⁻) or X can be any negatively charged radical such as sulfate(SO₄ ²⁻) and methosulfate (CH₃ SO₃ ⁻).

The formula indices have the following values: p has the value from 1 to6, q has the value from 0 to 6; r has the value 0 or 1; w has the value0 or 1, x has the value from 1 to 100; y has the value from 0 to 100; zhas the value 0 or 1; k is less than or equal to the value of n; m hasthe value from 4 to about 400, n has the value from 0 to about 200; m +nhas the value of at least 5.

The preferred modified polyamines comprise polyamine backbones whereinless than about 50% of the R groups comprise "oxy" R units, preferablyless than about 20%, more preferably less than 5%, most preferably the Runits comprise no "oxy" R units.

The most preferred polyamines which comprise no "oxy" R units comprisepolyamine backbones wherein less than 50% of the R groups comprise morethan 3 carbon atoms. For example, ethylene, 1,2-propylene, and1,3-propylene comprise 3 or less carbon atoms and are the preferred"hydrocarbyl" R units. That is when backbone R units are C₂ -C₁₂alkylene, preferred is C₂ -C₃ alkylene, most preferred is ethylene.

The polyamines of the present invention comprise modified homogeneousand non-homogeneous polyamine backbones, wherein 100% or less of the--NH units are modified. For the purpose of the present invention theterm "homogeneous polyamine backbone" is defined as a polyamine backbonehaving R units that are the same (i.e., all ethylene). However, thissameness definition does not exclude polyamines that comprise otherextraneous units comprising the polymer backbone which are present dueto an artifact of the chosen method of chemical synthesis. For example,it is known to those skilled in the art that ethanolamine may be used asan "initiator" in the synthesis of polyethyleneimines, therefore asample of polyethyleneimine that comprises one hydroxyethyl moietyresulting from the polymerization "initiator" would be considered tocomprise a homogeneous polyamine backbone for the purposes of thepresent invention. A polyamine backbone comprising all ethylene R unitswherein no branching Y units are present is a homogeneous backbone. Apolyamine backbone comprising all ethylene R units is a homogeneousbackbone regardless of the degree of branching or the number of cyclicbranches present.

For the purposes of the present invention the term "non-homogeneouspolymer backbone" refers to polyamine backbones that are a composite ofvarious R unit lengths and R unit types. For example, a non-homogeneousbackbone comprises R units that are a mixture of ethylene and1,2-propylene units. For the purposes of the present invention a mixtureof "hydrocarbyl" and "oxy" R units is not necessary to provide anon-homogeneous backbone. The proper manipulation of these "R unit chainlengths" provides the formulator with the ability to modify thesolubility and fabric substantivity of the modified polymers.

Preferred polyamines of the present invention comprise homogeneouspolyamine backbones that are totally or partially substituted bypolyethyleneoxy moieties, totally or partially quaternized amines,nitrogens totally or partially oxidized to N-oxides, and mixturesthereof. However, not all backbone amine nitrogens must be modified inthe same manner, the choice of modification being left to the specificneeds of the formulator. The degree of ethoxylation is also determinedby the specific requirements of the formulator.

The preferred polyamines that comprise the backbone of the compounds ofthe present invention are generally polyalkyleneamines (PAA's),polyalkyleneimines (PAI's), preferably polyethyleneamine (PEA's),polyethyleneimines (PEI's), or PEA's or PEI's connected by moietieshaving longer R units than the parent PAA's, PAI's, PEA's or PEI's. Acommon polyalkyleneamine (PAA) is tetrabutylenepentamine. PEA's areobtained by reactions involving ammonia and ethylene dichloride,followed by fractional distillation. The common PEA's obtained aretriethylenetetramine (TETA) and teraethylenepentamine (TEPA). Above thepentamines, i.e., the hexamines, heptamines, octamines and possiblynonamines, the cogenerically derived mixture does not appear to separateby distillation and can include other materials such as cyclic aminesand particularly piperazines. There can also be present cyclic amineswith side chains in which nitrogen atoms appear. See U.S. Pat. No.2,792,372, Dickinson, issued May 14, 1957, which describes thepreparation of PEA's.

Preferred amine polymer backbones comprise R units that are C₂ alkylene(ethylene) units, also known as polyethylenimines (PEI's). PreferredPEI's have at least moderate branching, that is the ratio of m to n isless than 4:1, however PEI's having a ratio of m to n of about 2:1 aremost preferred. Preferred backbones, prior to modification have thegeneral formula: ##STR29## wherein m and n are the same as definedherein above. Preferred PEI's, prior to modification, will have amolecular weight greater than about 200 daltons.

The relative proportions of primary, secondary and tertiary amine unitsin the polyamine backbone, especially in the case of PEI's, will vary,depending on the manner of preparation. Each hydrogen atom attached toeach nitrogen atom of the polyamine backbone chain represents apotential site for subsequent substitution, quaternization or oxidation.

These polyamines can be prepared, for example, by polymerizingethyleneimine in the presence of a catalyst such as carbon dioxide,sodium bisulfite, sulfuric acid, hydrogen peroxide, hydrochloric acid,acetic acid, etc. Specific methods for preparing these polyaminebackbones are disclosed in U.S. Pat. No. 2,182,306, Ulrich et al.,issued Dec. 5, 1939; U.S. Pat. No. 3,033,746, Mayle et al., issued May8, 1962; U.S. Pat. No. 2,208,095, Esselmann et al., issued Jul. 16,1940; U.S. Pat. No. 2,806,839, Crowther, issued Sep. 17, 1957; and U.S.Pat. No. 2,553,696, Wilson, issued May 21, 1951; all herein incorporatedby reference.

Examples of modified polyamines of the present invention comprisingPEI's, are illustrated in Formulas I-IV:

Formula I depicts a polymer comprising a PEI backbone wherein allsubstitutable nitrogens are modified by replacement of hydrogen with apolyoxyalkyleneoxy unit, --(CH₂ CH₂ O)₇ H, having the formula ##STR30##This is an example of a polymer that is fully modified by one type ofmoiety.

Formula II depicts a polymer comprising a PEI backbone wherein allsubstitutable primary amine nitrogens are modified by replacement ofhydrogen with a polyoxyalkyleneoxy unit, --(CH₂ CH₂ O)₇ H, the moleculeis then modified by subsequent oxidation of all oxidizable primary andsecondary nitrogens to N-oxides, said polymer having the formula##STR31##

Formula III depicts a polymer comprising a PEI backbone wherein allbackbone hydrogen atoms are substituted and some backbone amine unitsare quaternized. The substituents are polyoxyalkyleneoxy units, --(CH₂CH₂ O)₇ H, or methyl groups. The modified PEI polymer has the formula##STR32##

Formula IV depicts a polymer comprising a PEI backbone wherein thebackbone nitrogens are modified by substitution (i.e. by --(CH₂ CH₂ O)₇H or methyl), quaternized, oxidized to N-oxides or combinations thereof.The resulting polymer has the formula ##STR33##

In the above examples, not all nitrogens of a unit class comprise thesame modification. The present invention allows the formulator to have aportion of the secondary amine nitrogens ethoxylated while having othersecondary amine nitrogens oxidized to N-oxides. This also applies to theprimary amine nitrogens, in that the formulator may choose to modify allor a portion of the primary amine nitrogens with one or moresubstituents prior to oxidation or quaternization. Any possiblecombination of E groups can be substituted on the primary and secondaryamine nitrogens, except for the restrictions described herein above.

Detersive Surfactant Paste Or Acid Precursor

The process employs a surfactant paste in which a detersive surfactantand water are included. This surfactant paste typically has a viscosityof from about 5,000 cps to about 100,000 cps, more preferably from about10,000 cps to about 80,000 cps, and contains at least about 10% water,more typically at least about 30% water. The viscosity is measured at70° C. and at shear rates of about 10 to 100 sec.⁻¹. Alternatively, theprocess may employ a liquid acid precursor of an anionic detersivesurfactant which is eventually neutralized in the process to contain thesurfactant salt and water. Typically, this anionic surfactant will belinear alkylbenzene sulfonate. Optionally, other structuring agents,viscosity modifiers and various other minors may be included in thesurfactant paste or acid precursor thereof.

Nonlimiting examples of surfactants useful in the surfactant pasteinclude the conventional C₁₁ -C₁₈ alkyl benzene sulfonates ("LAS") andprimary, branched-chain and random C₁₀ -C₂₀ alkyl sulfates ("AS"), theC₁₀ -C₁₈ secondary (2,3) alkyl sulfates of the formula CH₃ (CH₂)_(x)(CHOSO3⁻ M⁺) CH₃ and CH₃ (CH2)_(y) (CHOSO₃ ⁻ M⁺)CH₂ CH₃ where x and(y+1) are integers of at least about 7, preferably at least about 9, andM is a water-solubilizing cation, especially sodium, unsaturatedsulfates such as oleyl sulfate, the C₁₀ -C₁₈ alkyl alkoxy sulfates("AE_(x) S"; especially EO 1-7 ethoxy sulfates), C₁₀ -C₁₈ alkyl alkoxycarboxylates (especially the EO 1-5 ethoxycarboxylates), the C₁₀₋₁₈glycerol ethers, and C₁₂ -C₁₈ alpha-sulfonated fatty acid esters ormixtures thereof.

If desired, the conventional nonionic and amphoteric surfactants may beincluded as adjunct surfactants in the surfactant paste which are theC₁₂ -C₁₈ alkyl ethoxylates ("AE") including the so-called narrow peakedalkyl ethoxylates and C₆ -C₁₂ alkyl phenol alkoxylates (especiallyethoxylates and mixed ethoxy/propoxy), C₁₂ -C₁₈ betaines; the C₁₀ -C₁₈alkyl polyglycosides and their corresponding sulfated polyglycosides,and sulfobetaines ("sultaines"), C₁₀ -C₁₈ amine oxides, and the like.The C₁₀ -C₁₈ N-alkyl polyhydroxy fatty acid amides can also be used.Typical examples include the C₁₂ -C₁₈ N-methylglucamides. See WO9,206,154. Other sugar-derived surfactants include the N-alkoxypolyhydroxy fatty acid amides, such as C₁₀ -C₁₈N-(3-methoxypropyl)glucamide. The N-propyl through N-hexyl C₁₂ -C₁₈glucamides can be used for low sudsing. C₁₀ -C₂₀ conventional soaps mayalso be used. If high sudsing is desired, the branched-chain C₁₀ -C₁₆soaps may be used. Mixtures of anionic and nonionic surfactants areespecially useful. Other conventional useful surfactants are listed instandard texts.

Dry Detergent Material

Dry detergent material such as sodium sulfate or other fillers and adetergent builder are also employed in the process to provide fullyformulated detergent compositions. The builder controls the effects ofmineral hardness during typical laundering operations. Inorganic as wellas organic builders can be used. Builders are typically used in fabriclaundering compositions to assist in the removal of particulate soils.The level of builder can vary widely depending upon the end use of thecomposition and its desired physical form. When present, thecompositions will typically comprise at least about 1% builder. Granularformulations typically comprise from about 10% to about 80%, moretypically from about 15% to about 50% by weight, of the detergentbuilder. Lower or higher levels of builder, however, are not meant to beexcluded.

Inorganic or P-containing detergent builders include, but are notlimited to, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate builders arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called "weak" builders(as compared with phosphates) such as citrate, or in the so-called"underbuilt" situation that may occur with zeolite or layered silicatebuilders.

Examples of silicate builders are the alkali metal silicates,particularly those having a SiO₂ :Na₂ O ratio in the range 1.6:1 to3.2:1 and layered silicates, such as the layered sodium silicatesdescribed in U.S. Pat. No. 4,664,839, issued May 12, 1987 to H. P.Rieck. NaSKS-6® is the trademark for a crystalline layered silicatemarketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlikezeolite builders, the Na SKS-6 silicate builder does not containaluminum. NaSKS-6 has the delta-Na₂ SiO₅ morphology form of layeredsilicate. It can be prepared by methods such as those described inGerman DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a highly preferredlayered silicate for use herein, but other such layered silicates, suchas those having the general formula NaMSi_(x) O_(2x+1)._(y) H₂ O whereinM is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, andy is a number from 0 to 20, preferably 0 can be used herein. Variousother layered silicates from Hoechst include NaSKS-5®, NaSKS-7® andNaSKS-11®, as the alpha, beta and gamma forms. As noted above, thedelta-Na₂ SiO₅ (NaSKS-6 form) is most preferred for use herein. Othersilicates may also be useful such as for example magnesium silicate,which can serve as a crisping agent in granular formulations, as astabilizing agent for oxygen bleaches, and as a component of sudscontrol systems.

Examples of carbonate builders are the alkaline earth and alkali metalcarbonates as disclosed in German Patent Application No. 2,321,001published on Nov. 15, 1973.

Aluminosilicate builders are useful in the present invention.Aluminosilicate builders are of great importance in most currentlymarketed heavy duty granular detergent compositions, and can also be asignificant builder ingredient in liquid detergent formulations.Aluminosilicate builders include those having the empirical formula:

    M.sub.z [(zAlO.sub.2).sub.y ].xH.sub.2 O

wherein z and y are integers of at least 6, the molar ratio of z to y isin the range from 1.0 to about 0.5, and x is an integer from about 15 toabout 264.

Useful aluminosilicate ion exchange materials are commerciallyavailable. These aluminosilicates can be crystalline or amorphous instructure and can be naturally-occurring aluminosilicates orsynthetically derived. A method for producing aluminosilicate ionexchange materials is disclosed in U.S. Pat. No. 3,985,669, Krummel, etal, issued Oct. 12, 1976. Preferred synthetic crystallinealuminosilicate ion exchange materials useful herein are available underthe designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. Inan especially preferred embodiment, the crystalline aluminosilicate ionexchange material has the formula:

    Na.sub.12 [(AlO.sub.2).sub.12 (SiO.sub.2).sub.12 ].xH.sub.2 O

wherein x is from about 20 to about 30, especially about 27. Thismaterial is known as Zeolite A. Dehydrated zeolites (x=0-10) may also beused herein. Preferably, the aluminosilicate has a particle size ofabout 0.1-10 microns in diameter.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to a wide variety ofpolycarboxylate compounds. As used herein, "polycarboxylate" refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Included among the polycarboxylate builders are a variety of categoriesof useful materials. One important category of polycarboxylate buildersencompasses the ether polycarboxylates, including oxydisuccinate, asdisclosed in Berg, U.S. Pat. No. 3,128,287, issued Apr. 7, 1964, andLamberti et al, U.S. Pat. No. 3,635,830, issued Jan. 18, 1972. See also"TMS/TDS" builders of U.S. Pat. No. 4,663,071, issued to Bush et al, onMay 5, 1987. Suitable ether polycarboxylates also include cycliccompounds, particularly alicyclic compounds, such as those described inU.S. Pat. Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903.

Other useful detergency builders include the etherhydroxypolycarboxylates, copolymers of maleic anhydride with ethylene orvinyl methyl ether, 1,3,5-trihydroxy benzene-2,4,6-trisulphonic acid,and carboxymethyloxysuccinic acid, the various alkali metal, ammoniumand substituted ammonium salts of polyacetic acids such asethylenediamine tetraacetic acid and nitrilotriacetic acid, as well aspolycarboxylates such as mellitic acid, succinic acid, oxydisuccinicacid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,carboxymethyloxysuccinic acid, and soluble salts thereof.

Citrate builders, e.g., citric acid and soluble salts thereof(particularly sodium salt), are polycarboxylate builders of particularimportance for heavy duty liquid detergent formulations due to theiravailability from renewable resources and their biodegradability.Citrates can also be used in granular compositions, especially incombination with zeolite and/or layered silicate builders.Oxydisuccinates are also especially useful in such compositions andcombinations.

Also suitable in the detergent compositions of the present invention arethe 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compoundsdisclosed in U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986. Usefulsuccinic acid builder include the C₅ -C₂₀ alkyl and alkenyl succinicacids and salts thereof. A particularly preferred compound of this typeis dodecenylsuccinic acid. Specific examples of succinate buildersinclude: laurylsuccinate, myristylsuccinate, paimitylsuccinate,2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like.Laurylsuccinates are the preferred builders of this group, and aredescribed in European Patent Application 86200690.5/0,200,263, publishedNov. 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Pat. No.4,144,226, Crutchfield et al, issued Mar. 13, 1979 and in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967. See also Diehl U.S. Pat. No.3,723,322.

Fatty acids, e.g., C₁₂ -C₁₈ monocarboxylic acids, can also beincorporated into the compositions alone, or in combination with theaforesaid builders, especially citrate and/or the succinate builders, toprovide additional builder activity. Such use of fatty acids willgenerally result in a diminution of sudsing, which should be taken intoaccount by the formulator.

In situations where phosphorus-based builders can be used, andespecially in the formulation of bars used for hand-launderingoperations, the various alkali metal phosphates such as the well-knownsodium tripolyphosphates, sodium pyrophosphate and sodium orthophosphatecan be used. Phosphonate builders such asethane-1-hydroxy-1,1-diphosphonate and other known phosphonates (see,for example, U.S. Pat. Nos. 3,159,581; 3,213,030; 3,422,021; 3,400,148and 3,422,137) can also be used.

Adjunct Detergent Ingredients

One or more adjunct detergent ingredients can be incorporated in thedetergent composition during subsequent steps of the present processinvention. These adjunct ingredients include other surfactants such ascationic surfactants, other detergency builders, suds boosters or sudssuppressers, anti-tarnish and anticorrosion agents, soil suspendingagents, soil release agents, germicides, pH adjusting agents,non-builder alkalinity sources, chelating agents such as diethylenetriamine penta acetic acid (DTPA) and diethylene triaminepenta(methylene phosphonic acid), smectite clays, enzymes,enzyme-stabilizing agents, dye transfer inhibitors and perfumes. SeeU.S. Pat. No. 3,936,537, issued Feb. 3, 1976 to Baskerville, Jr. et al.,incorporated herein by reference.

Other builders can be generally selected from the various water-soluble,alkali metal, ammonium or substituted ammonium phosphates,polyphosphates, phosphonates, polyphosphonates, carbonates, borates,polyhydroxy sulfonates, polyacetates, carboxylates, andpolycarboxylates. Preferred are the alkali metal, especially sodium,salts of the above. Preferred for use herein are the phosphates,carbonates, C₁₀ -C₁₈ fatty acids, polycarboxylates, and mixturesthereof. More preferred are sodium tripolyphosphate, tetrasodiumpyrophosphate, citrate, tartrate mono- and di-succinates, and mixturesthereof (see below).

In comparison with amorphous sodium silicates, crystalline layeredsodium silicates exhibit a clearly increased calcium and magnesium ionexchange capacity. In addition, the layered sodium silicates prefermagnesium ions over calcium ions, a feature necessary to insure thatsubstantially all of the "hardness" is removed from the wash water.These crystalline layered sodium silicates, however, are generally moreexpensive than amorphous silicates as well as other builders.Accordingly, in order to provide an economically feasible laundrydetergent, the proportion of crystalline layered sodium silicates usedmust be determined judiciously.

The crystalline layered sodium silicates suitable for use hereinpreferably have the formula

    NaMSi.sub.x O.sub.2x+1..sub.y H.sub.2 O

wherein M is sodium or hydrogen, x is from about 1.9 to about 4 and y isfrom about 0 to about 20. More preferably, the crystalline layeredsodium silicate has the formula

    NaMSi.sub.2 O.sub.5..sub.y H.sub.2 O

wherein M is sodium or hydrogen, and y is from about 0 to about 20.These and other crystalline layered sodium silicates are discussed inCorkill et al, U.S. Pat. No. 4,605,509, previously incorporated hereinby reference.

Specific examples of inorganic phosphate builders are sodium andpotassium tripolyphosphate, pyrophosphate, polymeric metaphosphatehaving a degree of polymerization of from about 6 to 21, andorthophosphates. Examples of polyphosphonate builders are the sodium andpotassium salts of ethylene diphosphonic acid, the sodium and potassiumsalts of ethane 1-hydroxy-1, 1-diphosphonic acid and the sodium andpotassium salts of ethane, 1,1,2-triphosphonic acid. Other phosphorusbuilder compounds are disclosed in U.S. Pat. Nos. 3,159,581; 3,213,030;3,422,021; 3,422,137; 3,400,176 and 3,400,148, all of which areincorporated herein by reference.

Examples of nonphosphorus, inorganic builders are tetraboratedecahydrate and silicates having a weight ratio of SiO₂ to alkali metaloxide of from about 0.5 to about 4.0, preferably from about 1.0 to about2.4. Water-soluble, nonphosphorus organic builders useful herein includethe various alkali metal, ammonium and substituted ammoniumpolyacetates, carboxylates, polycarboxylates and polyhydroxy sulfonates.Examples of polyacetate and polycarboxylate builders are the sodium,potassium, lithium, ammonium and substituted ammonium salts of ethylenediamine tetraacetic acid, nitrilotriacetic acid, oxydisuccinic acid,mellitic acid, benzene polycarboxylic acids, and citric acid.

Polymeric polycarboxylate builders are set forth in U.S. Pat. No.3,308,067, Diehl, issued Mar. 7, 1967, the disclosure of which isincorporated herein by reference. Such materials include thewater-soluble salts of homo- and copolymers of aliphatic carboxylicacids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid,aconitic acid, citraconic acid and methylene malonic acid. Some of thesematerials are useful as the water-soluble anionic polymer as hereinafterdescribed, but only if in intimate admixture with the non-soap anionicsurfactant.

Other suitable polycarboxylates for use herein are the polyacetalcarboxylates described in U.S. Pat. No. 4,144,226, issued Mar. 13, 1979to Crutchfield et al, and U.S. Pat. No. 4,246,495, issued Mar. 27, 1979to Crutchfield et al, both of which are incorporated herein byreference. These polyacetal carboxylates can be prepared by bringingtogether under polymerization conditions an ester of glyoxylic acid anda polymerization initiator. The resulting polyacetal carboxylate esteris then attached to chemically stable end groups to stabilize thepolyacetal carboxylate against rapid depolymerization in alkalinesolution, converted to the corresponding salt, and added to a detergentcomposition. Particularly preferred polycarboxylate builders are theether carboxylate builder compositions comprising a combination oftartrate monosuccinate and tartrate disuccinate described in U.S. Pat.No. 4,663,071, Bush et al., issued May 5, 1987, the disclosure of whichis incorporated herein by reference.

Suitable smectite clays for use herein are described in U.S. Pat. No.4,762,645, Tucker et al, issued Aug. 9, 1988, Column 6, line 3 throughColumn 7, line 24, incorporated herein by reference. Suitable additionaldetergency builders for use herein are enumerated in the Baskervillepatent, Column 13, line 54 through Column 16, line 16, and in U.S. Pat.No. 4,663,071, Bush et al, issued May 5, 1987, both incorporated hereinby reference.

In order to make the present invention more readily understood,reference is made to the following examples, which are intended to beillustrative only and not intended to be limiting in scope.

EXAMPLE I Preparation of PEI 1800 E₇

This Example illustrates a method by which one of the selected modifiedpolyamines is made. The ethoxylation is conducted in a 2 gallon stirredstainless steel autoclave equipped for temperature measurement andcontrol, pressure measurement, vacuum and inert gas purging, sampling,and for introduction of ethylene oxide as a liquid. A ˜20 lb. netcylinder of ethylene oxide (ARC) is set up to deliver ethylene oxide asa liquid by a pump to the autoclave with the cylinder placed on a scaleso that the weight change of the cylinder could be monitored.

A 750 g portion of polyethyleneimine (PEI) (Nippon Shokubai, EpominSP-018 having a listed average molecular weight of 1800 equating toabout 0.417 moles of polymer and 17.4 moles of nitrogen functions) isadded to the autoclave. The autoclave is then sealed and purged of air(by applying vacuum to minus 28" Hg followed by pressurization withnitrogen to 250 psia, then venting to atmospheric pressure). Theautoclave contents are heated to 130° C. while applying vacuum. Afterabout one hour, the autoclave is charged with nitrogen to about 250 psiawhile cooling the autoclave to about 105° C. Ethylene oxide is thenadded to the autoclave incrementally over time while closely monitoringthe autoclave pressure, temperature, and ethylene oxide flow rate. Theethylene oxide pump is turned off and cooling is applied to limit anytemperature increase resulting from any reaction exotherm. Thetemperature is maintained between 100 and 110° C. while the totalpressure is allowed to gradually increase during the course of thereaction. After a total of 750 grams of ethylene oxide has been chargedto the autoclave (roughly equivalent to one mole ethylene oxide per PEInitrogen function), the temperature is increased to 110° C. and theautoclave is allowed to stir for an additional hour. At this point,vacuum is applied to remove any residual unreacted ethylene oxide.

Next, vacuum is continuously applied while the autoclave is cooled toabout 50° C. while introducing 376 g of a 25% sodium methoxide inmethanol solution (1.74 moles, to achieve a 10% catalyst loading basedupon PEI nitrogen functions). The methoxide solution is sucked into theautoclave under vacuum and then the autoclave temperature controllersetpoint is increased to 130° C. A device is used to monitor the powerconsumed by the agitator. The agitator power is monitored along with thetemperature and pressure. Agitator power and temperature valuesgradually increase as methanol is removed from the autoclave and theviscosity of the mixture increases and stabilizes in about 1 hourindicating that most of the methanol has been removed. The mixture isfurther heated and agitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105° C. while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4500 g of ethylene oxide (resulting in a total of7 moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110° C. and themixture stirred for an additional hour.

The reaction mixture is then collected in nitrogen purged containers andeventually transferred into a 22 L three neck round bottomed flaskequipped with heating and agitation. The strong alkali catalyst isneutralized by adding 167 g methanesulfonic acid (1.74 moles). Thereaction mixture is then deodorized by passing about 100 cu. ft. ofinert gas (argon or nitrogen) through a gas dispersion frit and throughthe reaction mixture while agitating and heating the mixture to 130° C.The final reaction product is cooled slightly and collected in glasscontainers purged with nitrogen. In other preparations theneutralization and deodorization is accomplished in the reactor beforedischarging the product.

EXAMPLE II Formation of amine oxide of PEI 1800 E₇

This Example illustrates another method by which one of the selectedmodified polyamines is made. To a 500 mL Erlenmeyer flask equipped witha magnetic stirring bar is added polyethyleneimine having a molecularweight of 1800 and ethoxylated to a degree of about 7 ethoxy groups pernitrogen (PEI-1800, E₇) (209 g, 0.595 mole nitrogen, prepared as inExample I), and hydrogen peroxide (120 g of a 30 wt % solution in water,1.06 mole). The flask is stopped, and after an initial exotherm thesolution is stirred at room temperature overnight. ¹ H-NMR (D₂ O)spectrum obtained on a sample of the reaction mixture indicates completeconversion. The resonances ascribed to methylene protons adjacent tounoxidized nitrogens have shifted from the original position at ˜2.5 ppmto ˜3.5 ppm. To the reaction solution is added approximately 5 g of 0.5%Pd on alumina pellets, and the solution is allowed to stand at roomtemperature for approximately 3 days. The solution is tested and foundto be negative for peroxide by indicator paper. The material as obtainedis suitably stored as a 51.1% active solution in water.

EXAMPLE III Preparation of PEI 1200 E₇

This Example illustrates yet another method by which one of the selectedmodified polyamines is made. The ethoxylation is conducted in a 2 gallonstirred stainless steel autoclave equipped for temperature measurementand control, pressure measurement, vacuum and inert gas purging,sampling, and for introduction of ethylene oxide as a liquid. A ˜20 lb.net cylinder of ethylene oxide (ARC) is set up to deliver ethylene oxideas a liquid by a pump to the autoclave with the cylinder placed on ascale so that the weight change of the cylinder could be monitored. A750 g portion of polyethyleneimine (PEI) (having a listed averagemolecular weight of 1200 equating to about 0.625 moles of polymer and17.4 moles of nitrogen functions) is added to the autoclave. Theautoclave is then sealed and purged of air (by applying vacuum to minus28" Hg followed by pressurization with nitrogen to 250 psia, thenventing to atmospheric pressure). The autoclave contents are heated to130° C. while applying vacuum. After about one hour, the autoclave ischarged with nitrogen to about 250 psia while cooling the autoclave toabout 105° C. Ethylene oxide is then added to the autoclaveincrementally over time while closely monitoring the autoclave pressure,temperature, and ethylene oxide flow rate. The ethylene oxide pump isturned off and cooling is applied to limit any temperature increaseresulting from any reaction exotherm. The temperature is maintainedbetween 100 and 110° C. while the total pressure is allowed to graduallyincrease during the course of the reaction. After a total of 750 gramsof ethylene oxide has been charged to the autoclave (roughly equivalentto one mole ethylene oxide per PEI nitrogen function), the temperatureis increased to 110° C. and the autoclave is allowed to stir for anadditional hour. At this point, vacuum is applied to remove any residualunreacted ethylene oxide.

Next, vacuum is continuously applied while the autoclave is cooled toabout 50° C. while introducing 376 g of a 25% sodium methoxide inmethanol solution (1.74 moles, to achieve a 10% catalyst loading basedupon PEI nitrogen functions). The methoxide solution is sucked into theautoclave under vacuum and then the autoclave temperature controllersetpoint is increased to 130° C. A device is used to monitor the powerconsumed by the agitator. The agitator power is monitored along with thetemperature and pressure. Agitator power and temperature valuesgradually increase as methanol is removed from the autoclave and theviscosity of the mixture increases and stabilizes in about 1 hourindicating that most of the methanol has been removed. The mixture isfurther heated and agitated under vacuum for an additional 30 minutes.

Vacuum is removed and the autoclave is cooled to 105° C. while it isbeing charged with nitrogen to 250 psia and then vented to ambientpressure. The autoclave is charged to 200 psia with nitrogen. Ethyleneoxide is again added to the autoclave incrementally as before whileclosely monitoring the autoclave pressure, temperature, and ethyleneoxide flow rate while maintaining the temperature between 100 and 110°C. and limiting any temperature increases due to reaction exotherm.After the addition of 4500 g of ethylene oxide (resulting in a total of7 moles of ethylene oxide per mole of PEI nitrogen function) is achievedover several hours, the temperature is increased to 110° C. and themixture stirred for an additional hour. The reaction mixture is thencollected in nitrogen purged containers and eventually transferred intoa 22 L three neck round bottomed flask equipped with heating andagitation. The strong alkali catalyst is neutralized by adding 167 gmethanesulfonic acid (1.74 moles). The reaction mixture is thendeodorized by passing about 100 cu. ft. of inert gas (argon or nitrogen)through a gas dispersion frit and through the reaction mixture whileagitating and heating the mixture to 130° C. The final reaction productis cooled slightly and collected in glass containers purged withnitrogen. In other preparations the neutralization and deodorization isaccomplished in the reactor before discharging the product.

EXAMPLE IV

A modified polyamine is made in accordance with Example I ("PEI1800 E7")and used in the process of the current invention to form an agglomerateddetergent composition. An in-line static mixer is used into which thePEI1800 E7 is added continuously along with a sodium linear alkylbenzenesulfonate ("LAS") surfactant paste (60% LAS and balance water) at about60° C. in order to completely mix the ingredients, wherein the pH of thepremix is maintained at about 7 to 10. Thereafter, the premix arecontinuously fed to a high speed mixer/densifier (Lodige CB-30,commercially available from Lodige) along with sodium aluminosilicate(zeolite) and sodium carbonate. The rotational speed of the shaft in theLodige CB-30 mixer/densifier is about 1400 rpm and the mean residencetime is about 10 seconds. The contents from the Lodige CB-30mixer/densifer are continuously fed into a Lodige KM 600 mixer/densiferfor further agglomeration during which the mean residence time is about6 minutes. The detergent agglomerates are then screened withconventional screening apparatus resulting in a uniform particle sizedistribution. The composition of the detergent agglomerates exiting theis set forth in Table I below:

                  TABLE I                                                         ______________________________________                                        Component            % Weight                                                 ______________________________________                                        C.sub.12-13  linear alkylbenzene sulfonate                                                         29.1                                                     Sodium aluminosilicate                                                                             34.4                                                     Sodium carbonate     17.5                                                     Polyethylene glycol (MW 4000)                                                                       1.3                                                     PEI1800 E7            1.0                                                     Misc. (water, etc.)  15.7                                                                          100.0                                                    ______________________________________                                    

Performance testing for multi-cycle whiteness maintenance is conductedusing standard laundry testing techniques with test swatches of fabricswith various fiber contents. Unexpectedly, the agglomerated detergentcompositions made by a process in accordance with the invention whereinthe PEI1800 E7 is premixed with LAS in the premixer exhibitsignificantly improved cleaning performance compared to compositionsmade by process outside the scope of the present invention.

EXAMPLE V

A modified polyamine polymer is made in accordance with Example I("PEI1800E7") and used in another aspect of the current invention toform an agglomerated detergent composition. An in-line static mixer isused into which the PEI1800E7 is added continuously along with the acidform of linear alkylbenzene sulfonate ("HLAS") in order to form acompletely mixed premix. Thereafter the premix is continuously fed to ahigh speed mixer/densifier (Lodige CB-30, commercially available fromLodige), along with sodium carbonate and other dry detergent materials.Non-limiting examples of useful dry detergent materials include sodiumaluminosilicate (zeolite) sodium tripoly phosphate (STPP) and sodiumsulfate.

The rotational speed of the shaft in the Lodige CB-30 mixer/densifier isabout 1400 rpm and the mean residence time about 10 seconds. Thecontents from Lodige CB-30 mixer/densifier are continuously fed into aLodige KM-600 mixer/densifier for further agglomeration during which themean residence time is about 6 minutes. The detergent agglomerates arethen screened with conventional screening apparatus resulting in auniform particle size distribution. The composition of the detergentagglomerates exiting is set forth in Table 2 below:

                  TABLE 2                                                         ______________________________________                                        Component            % Weight                                                 ______________________________________                                        C.sub.12-13  linear alkylbenzene sulfonate                                                         20.0%                                                    Sodium Carbonate     18.0%                                                    PEI1800E7             0.5%                                                    Sodium aluminosilicate                                                                             16.0%                                                    Sodium tripoly phosphate                                                                           35.0%                                                    Sodium sulfate        3.5%                                                    Misc. (Water, etc.)   7.0%                                                    Total:               100.0%                                                   ______________________________________                                    

Performance testing for multi-cycle whiteness maintenance is conductedusing standard laundry testing techniques with test swatches of fabricswith various fiber contents. Unexpectedly, the agglomerated detergentcompositions made by a process in accordance with this aspect of theinvention wherein the PEI1800E7 is premixed with the HLAS in thepremixer exhibits significantly improved cleaning performance comparedto compositions made by process outside the scope of the presentinvention.

Having thus described the invention in detail, it will be clear to thoseskilled in the art that various changes may be made without departingfrom the scope of the invention and the invention is not to beconsidered limited to what is described in the specification.

What is claimed is:
 1. A process for producing an agglomerated detergentcomposition comprising the steps of:(a) premixing an acid precursor of adetersive surfactant, and a water-soluble or dispersible, modifiedpolyamine in a mixer to form a premix, said modified polyamine having apolyamine backbone prior to modification via quaternization,substitution or oxidation corresponding to the formula: ##STR34## andwherein the modified polyamine has the formula V.sub.(n+1) W_(m) Y_(n) Zor a polyamine backbone prior to modification via quaternization,substitution or oxidation corresponding to the formula: ##STR35## andwherein the modified polyamine has the formula V.sub.(n-k+1) W_(m) Y_(n)Y'_(k) Z, wherein k is less than or equal to n, said polyamine backboneprior to modification has a molecular weight greater than about 200daltons, whereini) V units are terminal units having the formula:##STR36## ii) W units are backbone units having the formula: ##STR37##iii) Y units are branching units having the formula: ##STR38## iv) Y'units are branching units having the formula: ##STR39## v) Z units areterminal units having the formula: ##STR40## wherein backbone linking Runits are selected from the group consisting of C₂ -C₁₂ alkylene, C₄-C₁₂ alkenylene, C₃ -C₁₂ hydroxyalkylene, C₄ -C₁₂ dihydroxy-alkylene, C₈-C₁₂ dialkylarylene, --(R¹ O)_(x) R¹ --, --(R¹ O)_(x) R⁵ (OR¹)_(x) --,--(CH₂ CH(OR²)CH₂ O)_(z) (R¹ O)_(y) R¹ (OCH₂ CH(OR²)CH₂)_(w) --,--C(O)(R⁴)_(r) C(O)--, --CH₂ CH(OR²)CH₂ --, and mixtures thereof;wherein R¹ is C₂ -C₆ alkylene and mixtures thereof; R² is hydrogen,--(R¹ O)_(x) B, and mixtures thereof; R⁴ is C₁ -C₁₂ alkylene, C₄ -C₁₂alkenylene, C₈ -C₁₂ arylalkylene, C₆ -C₁₀ arylene, and mixtures thereof;R⁵ is C₁ -C₁₂ alkylene, C₃ -C₁₂ hydroxyalkylene, C₄ -C₁₂dihydroxy-alkylene, C₈ -C₁₂ dialkylarylene, --C(O)--, --C(O)NHR⁶NHC(O)--, --R¹ (OR¹) --, --C(O)(R⁴)_(r) C(O)--, --CH₂ CH(OH)CH₂ --,--CH₂ CH(OH)CH₂ O(R¹ O)_(y) R¹ OCH₂ CH(OH)CH₂ --, and mixtures thereof;R⁶ is C₂ -C₁₂ alkylene or C₆ -C₁₂ arylene; E units are selected from thegroup consisting of hydrogen, C₁ -C₂₂ alkyl, C₃ -C₂₂ alkenyl, C₇ -C₂₂arylalkyl, C₂ -C₂₂ hydroxyalkyl, --(CH₂)_(p) CO₂ M, --(CH₂)_(q) SO₃ M,--CH(CH₂ CO₂ M)CO₂ M, --(CH₂)_(p) PO₃ M, --(R¹ O)_(x) B, --C(O)R³, andmixtures thereof; R³ is C₁ -C₁₈ alkyl, C₇ -C₁₂ arylakyl, C₇ -C₁₂ alkylsubstituted aryl, C₆ -C₁₂ aryl, and mixtures thereof; B is hydrogen, C₁-C₆ alkyl, --(CH₂)_(q) SO₃ M, --(CH₂)_(p) CO₂ M, --(CH₂)_(q) (CHSO₃M)CH₂ SO₃ M, --(CH₂)_(q) --(CHSO₂ M)CH₂ SO₃ M, --(CH₂)_(p) PO₃ M, --PO₃M, and mixtures thereof; M is hydrogen or a water soluble cation insufficient amount to satisfy charge balance; X is a water soluble anion;m has the value from 4 to about 400; n has the value from 0 to about200; p has the value from 1 to 6, q has the value from 0 to 6; r has thevalue of 0 or 1; w has the value 0 or 1; x has the value from 1 to 100;y has the value from 0 to 100; z has the value 0 or 1; (b) inputtingsaid premix and dry detergent material into a high speed mixer/densifierand neutralizing said acid precursor to form agglomerates; and (c)agglomerating said agglomerates further in a moderate speedmixer/densifier so as to form said detergent composition.
 2. The processof claim 1 wherein the pH of said premix is in a range from about 1 toabout
 3. 3. The process of claim 1 wherein said modified polyamine ispresent in an amount of from 0.01% to about 10% by weight of saiddetergent composition.
 4. The process of claim 1 wherein said premixingstep is performed in a temperature range of from about 50° C. to about90° C.
 5. The process of claim 1 wherein said inputting step includesthe step of adding a neutralizing agent selected from the groupconsisting of sodium carbonate, sodium hydroxide, sodium silicate andmixtures thereof to said high speed mixer/densifier so as to neutralizesaid acid precursor.
 6. The process of claim 5 wherein said neutralizingagent is sodium carbonate.
 7. The process of claim 1 further comprisingthe step of drying said agglomerates.
 8. The process of claim 1 whereinsaid agglomerates have a density of at least about 650 g/l.
 9. Theprocess of claim 1 wherein R is C₂ -C₁₂ alkylene.